Hydrazine sweetening



the aromatic mercaptan in the catalyst solution.

United States Patent w 3,15%,570 HYDRAZENE SWEETENING Charles 0. letty, R0. Box 846, Tyler, Tex. Filed Dec. 10, 1962, Ser. No. 246,281 6 (Iiaims. (til. 208-2d6) This invention relates to air sweetening of sour naphthas with mercaptan catalyzed spent caustic containing acid oils and, more particularly, to the use of hydrazine to stabilize the catalyst caustic solution against foaming and rapid depletion of the anomatic mercaptan as well as acid oils in the catalyst solution by air oxidation, and to improve overall sweetening economy by the use of hydrazine stabilized mercaptan in the catalyst solution.

In my prior co-pending application, Serv No. 860,601, filed December 18, 1959, now Patent No. 3,092,569, of which the present applicationis a continuation-in-part, I have disclosed the improved effect of aromatic mercaptan in spent caustic to catalyze air sweetening of sour distillate, that caustic catalyst solution also containing phenolic acid oils and usually derived from spent caustic.

That method, whileit represented an important economy because it used very economically available sweetening components such as spent caustic and acid'oils and even aromatic mercaptans by further processing, all available from preliminary caustic wash treatments of sour distillates, had certain disadvantages;

For one thing, the continuous passage of air through high acid oil containing spent caustic catalyst tended to cause substantial foaming which resulted either in short cycles of use of the caustic catalysts wash tower, each requiring replacement with a fresh catalyst solution, or necessitating the use of a second wash tower to capture the foamed carryover. That second'wash tower, usually a caustic wash, intended to remove slight contaminating catalyst solution, itself became'contaminated too rapidly by the foam carryover. While various commercial defoamers, notably silicones and higher alcohols and alkanol amines, have been tried with some defoaming success, these have been unduly expensive for efiecting that single function and resulted in large reduction in the economy of that method.

Moreover, the continuous passage of air in large quantity through the catalyst solution tended rapidlyto oxidize the aromatic mercaptan which in the disulfide form becomes inactivated as a sweetening catalyst and requires rapid replenishment, thereby increasing the expense of the method despite the fact that it could be made available from preliminary wash solutions. The phenolic acid oils, also essentially present in the catalytic solution, also be come oxidized in continuous wash contact with the air used for sweetening.

According to the present invention I have now found oxidized by the air, the products are merely inert nitrogen and water.

In applying my improved sweetening to treatment of V a light catalytic sour naphtha, after subjecting it to a preliminary caustic wash with a 20 to 50 B. caustic, the naphtha, flowing at about a rate of 75 to 100 gallons per minute, has added to it about to 1% cubic feet of air per minute, and is passed countercurrently through the catalytic scrubber in which the catalytic caustic aromatic mercaptan and hydrazine solution is rapidly circu lated. The scrubbed and thus simply sweetened light catalytic naphtha is then merely given a water wash and is ready for use as a sweetened naphtha. From time to time the preliminary caustic wash solution has portions withdrawn and regenerated by passing air therethrough at 175 F, and then returning the regenerated caustic solution tojthe preliminary wash scrubbing tower. The catalytic scrubber solution consists of to 40 Be. caustic in water containing 5 to 30 volume percent of acid oils, from 0.01 to 3 weight percent of arylmercaptaus, typically phenyl or tolyl mercaptans. The catalyst solution further has added about 0.0001 to 0.2% of hydrazine. The caustic, the phenolic acid oils and/or the mercaptan can a each be obtained by processing preliminary spent caustic I passed at a rate of about 10 to gallons per minute" that the addition of very small quantitiesof hydrazine to ing. Again, in the instance of easily sweetened naphthas such as light catalytically cracked naphtha, a second caustic-containing wash tower may be eliminated, and the catalyst in the second wash tower substituted by an ordinary water washing following the single caustic-mersolutions as described in my parent application. They may also be obtained from other commercial sources.

In operation, the catalyst solution has continuously or intermittently injected therein a diluted solution of hydrazine to impart a minute hydrazine content to the catalyst solution. Preferably the re-circulating catalyst scrubber solution has slowly injected therein a 3 to 6% aqueous hydrazine solution at the rate of about 3 to 6 pounds of hydrazine per day, which would provide a very minute content of hydrazine in the catalyst scrubber solution, usually less than 0.2% and generally even less than 0.0003%. A typical hydrazine content in the caustic scrubber solution is between about 0.0001% and 0.0003% by weight of the catalyst solution, and while the use of the larger quantities gives some improved sweetening it is much less economical. 1, I

'In the treatment of sour coker or thermal gasolines, more dihicult to sweeten, and having a higher content of aliphatic mercaptans, the naphtha, after being first given a pro-wash with 20 to 40 B. caustic solution, is

together with 1 to 2 cubic feet per minute of air through a first catalyst solution, which need not be circulated because a'second catalytic contact is preferably applied to such diflicultlysweetened naphtha. Moreover, the hydrazine, added in the same quantity as in the catalytic naphtha sweetening, can be injected into the top of the tower so that some may be carried over with the naphtha to a second scrubbing tower in which the catalytic solution is circulated. The twice catalyst treated coker or thermal naphtha is then given a final caustic wash and then a water wash.

The process is further illustrated in the drawings herein:

FIG. 1 shows diagrammatically a flow sheet for sweetening of light catalytic gasoline; and

FIG. 2 shows such flow sheet for sweetening of coker or thermal gasoline.

Referring first to FIG. 1, the catalytic gasoline enters the system through line 10 impelled by a pump 12 and passes-to caustic pre-wash tower 14 which would contain the 20 to 50% aqueous caustic B. solution. The caustic mixture for washing naphtha is withdrawn through a line 16 controlled by a valve 18 and recirculated to the upper end of the tower 14 through line 22 as impelled by a pump in a continuous rapid washing circulation. The treated pre-washed gasoline leaves overhead through line 28 and is mixed with air entering through line 36 as metered at 34 through valve 32, and the air mixed with the pre-washed gasoline enters through line 29 into the catalyst tower 30. The catalyst solution is withdrawn rom the bottom of scrubber 30 through line 38 controlled by valve 40 and is re-circulated to' a point near the top of the scrubber through line 44 as impelled by pump 42. The catalytically scrubbed naphtha then passes overhead through line 50. From time to time aryl thiol catalyst is added to the system through line 46 impelled by pump 47 to maintain the desired aromatic mercaptan content in the catalyst solution. Hydrazine solution is passed into line 44 by way of line impelled by a proportioning pump 49 to impart the desired hydrazine content to the catalyst solution. The catalytically sweetened naphtha enters a second scrubber 52 from line 50 and is here usually scrubbed only with water, which can be re-circulated by way of line 54, valve 56, pump 58, and line 60. The scrubber 52 could also be used with catalyst solution and operated like scrubber 30, but this is generally not necessary with light catalytically cracked gasolines which are easy to sweeten. The scrubber sweetened naphtha in tower 52 leaves overhead through line 62 and passes to a settler 64 from which any caustic contaminated water is settled out, the naphtha being passed by line 66 through a second water washing scrubber 68, fresh wash water entering at 70 and being withdrawn at the bottom through line 72 controlled by valve 74. The sweetened washed catalytic naphtha leaves overhead through line 76, passing thence to storage.

For the treatment of more difiicult to sweeten naphthas such as coker or thermal gasoline, as shown in FIG. 2, the naphtha enters a caustic pro-wash tank 84 through line as impelled by pump 82. The caustic pre-wash solution is circulated by being withdrawn through the bottom at line 88 controlled by valve 90 and returned to a point near the top through line 86 as impelled by a pump 87. The caustic pre-washed naphtha passes overhead through line 96 and is mixed with a quantity of air entering line 106 metered at 102 through valve 100, the flow being further controlled by valve 104. The air and naphtha mixture in line 97 enters the catalytic scrubber 98, where it is contacted with the catalytic solution. That catalyst solution is adjusted in aromatic mercaptan content entering through line impelled by a pump 12.2.as controlled by valve 110. Similarly, hydrazine solution is passed into the system through line 114 by pump 118. The once catalytically scrubbed naphtha leaving overhead through line 116 enters a second scrubber 128 in which the catalyst mixture is withdrawn at the bottom through line 130 controlled by a valve 132 and returned to a point near the top by a line 136 as impelled by a pump 134. Additional hydrazine is passed into the second circulating catalyst solution through line as impelled by a pump 108. The twice scrubbed and sweetened naphtha passes overhead in line 156 to a final wash tower 158 where it is contacted with fresh wash water entering through line 160 near the top, the wash water being withdrawn at the bottom through line 162 as controlled by valve 164. The sweetened thermal or coker naphtha leaves the system through line 166, passing thence to storage.

The caustic in the pro-wash towers 14 and 84 is withdrawn from time to time, as shown in FIG. 1, through line 24 as controlled by valve 26, or, as shown in FIG. 2, by line 2 controlled by valve 94. The spent caustic is regenerated by passing air pre-heated to about F.

The following examples illustrate details of sweetening of various naphthas. 1

EXAMPLE I A light catalytically cracked gasoline containing .004 weight percent RSH, as sulfur, is first pro-washed with 35 Be. caustic soda solution and then passed at a rate of 86 gallons per minute together with 1 cubic foot of air per minute countercnrrently through a washing tower of caustic solution containing aromatic mercaptan, hydrazine and acid oils, catalyst. The catalyst is circulated countercurrently in wash contact with the air and naphtha from top to bottom against the naphtha at a rate between 13 and 14 gallons per minute. The catalyst consists of 35 B. caustic containing 25 volume percent acid oils obtained from spent caustic pre-washing of cracked naphthas to which had been added 3 weight percent of mixed phenyl and tolyl mercaptan. Into the circulating catalyst solution and scrubber there is injected /2 gallon 4.3 pounds per day of 44.8% hydrazine which has been diluted for handling to a total of 5 /2 gallons with water. It is found that no foaming takes place in the catalyst scrubber solution. The RSH sulfur is reduced from about 0.0006% to 0.0002% on the average. The color of the light catalytic naphtha is likewise improved in the wash, being reduced from 135 or poorer down to-35. No second caustic scrubber is used in this treatment of the catalytically cracked naphtha, the treatment following the catalyst scrubbing consisting merely of a water wash.

EXAMPLE II On a laboratory scale 5 ml. of the same light catalytic gasoline was placed in a gas scrubbing bottle to which was added 2 00 ml. of catalytic spent caustic containing 3 weight percent of aryl mercaptans and 36 volume percent of phenols, and 200 ml. of 50 B. caustic soda in water. Air was passed into the liquid mixture through a fitted glass dispersion tube at a rate fast enough to effect a mixture. Samples were run with and without hydrazine. The following table shows in tabular form the results obtained.

' Distilled Water=0.

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Thermally cracked gasoline of 12s to 430 F. B.P. containing 0.024 weight percent RSH as sulfur is sweet- 75 ened by first passing it through a caustic pre-wash tower solution was exhausted in about days and needed replenishment.

to days elapsed before the aryl mercaptan was comparatively exhausted. Again, in each instance the quality instance of the control, having no additive to protect the aryl mercaptan, the latter was reduced after 96 hours to 0.04- weight percent. It is apparent that the effect of the hydrazine to stabilize the aryl mercaptan is substantial and far more effective than a standard reducing agent such as sodium sulfite, even though the sulfite was used in much greater quantity.

EXAMPLE IV the condition of the catalyst solution and the quality of the light catalytic gasoline produced is analyzed every other day. A comparison is given of three plant runs both before and after hydrazine injection.

containing 35 B. caustic. The gasoline is flowed through a first scrubber at a rate of 25 gallons per minute together with 1 /2 cubic feet of air. The scrubber contains 25 volume percent of acid oil in 35 B. caustic having an aryl mercaptan content of 2.0 weight percent. The caustic is not recirculated, but instead into the top of the scrubber tower is injected 4 gallon per day of 44.8 weight percent hydrazine in water. After leaving the first catalytic scrubbing tower, the partially sweetened thermal gasoline is passed to a second scrubber which contains 35 B. caustic having 30 weight percent of acid oil and 2 weight percent of aryl mercaptans. The caustic in this second tower is recirculated from the bottom to the top at a rate of 800 gallons per hour and more of the same hydrazine solution is injected into the second scrubber tower at the same rate of gallon per day. For ease of handling, the A gallon of 44.8 weight percent hydrazine may be diluted with 5 gallons of water.

The following table illustrates approximate costs and comparable data obtained in the several treatments inciuding the one of this example.

Table IV Lt. Cat. Gasoline Thermal-(Joker Before After Before After Caustic Used, lbs/m0 18, 000 1, 800 20, 000 G, 000 Total Treating Cost, c./bbl 1.0 0. 4 4. 0 2.0 Percent RSl-I Average 0. 0006 0. 0002 0. 0009 0.0003 Color Average 135 35 300 135 Air Rate it. /uii11 3.0 1.0 3. 0 1.0

point of the naphtha under the pressure of the system, to the caustic catalytic solution or the naphtha or both during the sweetening, and, consequently, while the present process is adapted for operation at moderate or ambient temperatures, heat can be applied. The system is usually operated at a moderate pumping pressure which can be increased or decreased slightly depending upon useful refinery pressures.

I claim:

1. The method of sweetening a sour hydrocarbon naphtha containing a small quantity of sour components comprising scrubbing the said sour naphtha with a catalyst solution containing strong aqueous caustic, from 0.01 to 3 weight percent of aromatic mercapta ns, at least 10 volume percent of acid oils, and a small quantity of hydrazine in the presence of an oxygen-containing gas.

2. The method as defined in claim 1 wherein the naphtha is catalytically cracked naphtha.

3. The method as defined in claim 1 wherein the naphtha is thermally cracked naphtha.

4. The method as defined in claim 1 wherein the sour naphtha is first pro-washed with strong aqueous caustic.

5. The method of sweetening sour hydrocarbon naphcontaining a small quantity of sour components, comprising first pre-washing the sour naphthas with strong 20-50 B. aqueous caustic and then scrubbing the naphtha with a to B. caustic catalyst solution containing from .01 to 3 weight percent of aromatic mercaptans, 5 to 35 volume percent of phenolic acid oils, and a trace of hydrazine in the presence of 1 to 3 cu. ft. per min. of air passed into the naphtha while scrubbing at a rate of 13 to gallons per minute.

6. The method as defined in claim 5 wherein the sour naphtha is a difiicultly sweetened thermal gasoline and is subjected to a second catalytic scrubbing treatment following the first eatalytic scrubber treatment.

References Cited in the file of this patent UNITED STATES PATENTS 2,862,804 Petty Dec. 2, 1958 2,930,750 Wendland Mar. 29, 1960 3,092,569 Petty June 4, 1963 

1. THE METHOD OF SWEETENING A SOUR HYDROCARBON NAPHTHA CONTAINING A SMALL QUANTITY OF SOUR COMPONENTS COMPRISING SCRUBBING THE SAID SOUR NAPHTHA WITH A CATALYST SOLUTION CONTAINING STRONG AQUEOUS CAUSTIC, FROM 0.01 TO 3 WEIGHT PERCENT OF AROMATIC MERCAPTANS, AT LEAST 10 VOLUME PERCENT OF ACID OIL, AND A SMALL QUANTITY OF HYDRAZINE IN THE PRESENCE OF AN OXYGEN-CONTAINING GAS. 